Diferulic acids

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Diferulic acids (also known as dehydrodiferulic acids) are organic compounds that have the general chemical formula C20H18O8, they are formed by dimerisation of ferulic acid. Curcumin and curcuminoids, though having a structure resembling diferulic acids', are not formed that way but through a condensation process. Just as ferulic acid is not the proper IUPAC name, the diferulic acids also tend to have trivial names that are more commonly used than the correct IUPAC name. Diferulic acids are found in plant cell walls, particularly those of grasses.

Dimer (chemistry) Oligomer consisting of two monomers joined by bonds that can be either strong or weak, covalent or intermolecular

A dimer is an oligomer consisting of two monomers joined by bonds that can be either strong or weak, covalent or intermolecular. The term homodimer is used when the two molecules are identical and heterodimer when they are not. The reverse of dimerisation is often called dissociation. When two oppositely charged ions associate into dimers, they are referred to as Bjerrum pairs.

Ferulic acid chemical compound

Ferulic acid is a hydroxycinnamic acid, an organic compound. It is an abundant phenolic phytochemical found in plant cell walls, covalently bonded as side chains to molecules such as arabinoxylans. As a component of lignin, ferulic acid is a precursor in the manufacture of other aromatic compounds. The name is derived from the genus Ferula, referring to the giant fennel.

Curcumin chemical compound

Curcumin is a bright yellow chemical produced by Curcuma longa plants. It is the principal curcuminoid of turmeric, a member of the ginger family, Zingiberaceae. It is sold as an herbal supplement, cosmetics ingredient, food flavoring, and food coloring.

Contents

Structures

There are currently nine known structures for diferulic acids. [1] They are usually named after the positions on each molecule that form the bond between them. Included in the group are 8,5'-DiFA (DC) (or decarboxylated form) and 8,8'-DiFA (THF) (or tetrahydrofuran form), which are not true diferulic acids, but probably have a similar biological function. The 8,5'-DiFA (DC) lost CO2 during its formation, the 8,8'-DiFA (THF) gained H2O during its formation. 8,5'-DiFA (BF) is the benzofuran form.

Benzofuran chemical compound

Benzofuran is the heterocyclic compound consisting of fused benzene and furan rings. This colourless liquid is a component of coal tar. Benzofuran is the "parent" of many related compounds with more complex structures. For example, psoralen is a benzofuran derivative that occurs in several plants.

Ferulic acid can also form trimers and tetramers, known as triferulic and tetraferulic acids respectively. [2]

Chemical structures of nine known diferulic acids DiferulicAcids.svg
Chemical structures of nine known diferulic acids

Occurrences

They have been found in the cell walls of most plants, but are present at higher levels in the grasses (Poaceae) and also sugar beet and Chinese water chestnut. [3]

Poaceae family of plants

Poaceae or Gramineae is a large and nearly ubiquitous family of monocotyledonous flowering plants known as grasses, commonly referred to collectively as grass. Poaceae includes the cereal grasses, bamboos and the grasses of natural grassland and cultivated lawns and pasture.

Sugar beet Plant grown commercially for sugar production

A sugar beet is a plant whose root contains a high concentration of sucrose and which is grown commercially for sugar production. In plant breeding it is known as the Altissima cultivar group of the common beet. Together with other beet cultivars, such as beetroot and chard, it belongs to the subspecies Beta vulgaris subsp. vulgaris. Its closest wild relative is the sea beet.

The 8-O-4'-DiFA tends to predominate in grasses, but 5,5'-DiFA predominates in barley bran. [4] [5] Rye bread contains ferulic acid dehydrodimers. [6]

Rye bread type of bread made with various proportions of flour from rye grain

Rye bread is a type of bread made with various proportions of flour from rye grain. It can be light or dark in color, depending on the type of flour used and the addition of coloring agents, and is typically denser than bread made from wheat flour. It is higher in fiber than white bread and is often darker in color and stronger in flavor.

In chufa (tiger nut, Cyperus esculentus) and sugar beet the predominant diferulic acids are 8-O-4'-DiFA and 8,5'-DiFA respectively. [7] [8] 8-5' Non cyclic diferulic acid has been identified to be covalently linked to carbohydrate moieties of the arabinogalactan-protein fraction of gum arabic. [9]

<i>Cyperus esculentus</i> species of plant in the sedge family Cyperaceae

Cyperus esculentus is a crop of the sedge family widespread across much of the world. It is found in most of the Eastern Hemisphere, including Southern Europe, Africa and Madagascar, as well as the Middle East and the Indian subcontinent. C. esculentus is cultivated for its edible tubers, called earth almonds or tiger nuts, as a snackfood and for the preparation of horchata de chufa, a sweet, milk-like beverage.

8,5-Diferulic acid chemical compound

8,5'-Diferulic acid is a non cyclic type of diferulic acid. It is the predominant diferulic acid in sugar beet pulp. It is also found in barley, in maize bran and rye. 8-5'-Diferulic acid has also been identified to be covalently linked to carbohydrate moieties of the arabinogalactan-protein fraction of gum arabic.

Gum arabic Natural gum consisting of the hardened sap of various species of the acacia tree

Gum arabic, also known as gum sudani, acacia gum, arabic gum, gum acacia, acacia, Senegal gum and Indian gum, and by other names, is a natural gum consisting of the hardened sap of various species of the acacia tree. Gum arabic is collected from acacia species, predominantly Acacia senegal and Vachellia (Acacia) seyal. The term "gum arabic" does not indicate a particular botanical source. In a few cases so‐called "gum arabic" may not even have been collected from Acacia species, but may originate from Combretum, Albizia or some other genus. The gum is harvested commercially from wild trees, mostly in Sudan (80%) and throughout the Sahel, from Senegal to Somalia—though it is historically cultivated in Arabia and West Asia.

Function

Diferulic acids are thought to have a structural function in plant cell walls, where they form cross-links between polysaccharide chains. They have been extracted attached to a few sugar molecules at both ends, but so far no definitive proof of them linking separate polysaccharide chains has been found. [10] In suspension-cultured maize cells, dimerisation of ferulic acid esterified to polysaccharides occurs mostly in the protoplasm, but may occur in the cell walls when peroxide levels increase due to pathogenesis. [11] In suspension-cultured wheat cells, only the 8,5'-diferulic acid is formed intraprotoplasmically with the other dimers being formed in the cell wall. [12]

Preparation

Most diferulic acids are not commercially available and must be synthesised in lab. Synthetic routes have been published, but it is often simpler to extract them from plant material. They can be extracted from plant cell walls (often maize bran) by concentrated solutions of alkali, the resulting solution is then acidified and phase separated into an organic solvent. The resulting solution is evaporated to give a mixture of ferulic acid moieties that can be separated by column chromatography. Identification is often by high performance liquid chromatography with a UV detector or by LC-MS. Alternatively they can be derivatised to make them volatile and therefore suitable for GC-MS. Curcumin can be hydrolyzed (alkaline) to yield two molecules of ferulic acid. Peroxidases can produce dimers of ferulic acid, in the presence of hydrogen peroxide through radical polymerization. [13]

Uses

Diferulic acids are more effective inhibitors of lipid peroxidation and better scavengers of free radicals than ferulic acid on a molar basis. [14]

History

The first diferulic acid discovered was the 5,5'-diferulic acid, and for a while this was thought to be the only one. [15]

See also

Related Research Articles

Carbohydrate Organic compound that consists only of carbon, hydrogen, and oxygen

A carbohydrate is a biomolecule consisting of carbon (C), hydrogen (H) and oxygen (O) atoms, usually with a hydrogen–oxygen atom ratio of 2:1 (as in water) and thus with the empirical formula Cm(H2O)n (where m may be different from n). This formula holds true for monosaccharides. Some exceptions exist; for example, deoxyribose, a sugar component of DNA, has the empirical formula C5H10O4. The carbohydrates are technically hydrates of carbon; structurally it is more accurate to view them as aldoses and ketoses.

Glucose A simple form of sugar

Glucose is a simple sugar with the molecular formula C6H12O6. Glucose is the most abundant monosaccharide, a subcategory of carbohydrates. Glucose is mainly made by plants and most algae during photosynthesis from water and carbon dioxide, using energy from sunlight. There it is used to make cellulose in cell walls, which is the most abundant carbohydrate. In energy metabolism, glucose is the most important source of energy in all organisms. Glucose for metabolism is partially stored as a polymer, in plants mainly as starch and amylopectin and in animals as glycogen. Glucose circulates in the blood of animals as blood sugar. The naturally occurring form of glucose is d-glucose, while l-glucose is produced synthetically in comparatively small amounts and is of lesser importance. Glucose is a monosaccharide containing six carbon atoms and an aldehyde group and is therefore referred to as an aldohexose. The glucose molecule can exist in an open-chain (acyclic) and ring (cyclic) form, the latter being the result of an intramolecular reaction between the aldehyde C atom and the C-5 hydroxyl group to form an intramolecular hemiacetal. In water solution both forms are in equilibrium and at pH 7 the cyclic one is the predominant. Glucose is a primary source of energy for living organisms. It is naturally occurring and is found in fruits and other parts of plants in its free state. In animals glucose arises from the breakdown of glycogen in a process known as glycogenolysis.

Hemicellulose structural polymer in plant cell walls

A hemicellulose is one of a number of heteropolymer, such as arabinoxylans, present along with cellulose in almost all terrestrial plant cell walls. While cellulose is crystalline, strong, and resistant to hydrolysis, hemicelluloses have random, amorphous structure with little strength. They are easily hydrolyzed by dilute acid or base as well as a myriad of hemicellulase enzymes.

Phenols chemical compounds in which hydroxyl group is attached directly to an aromatic ring

In organic chemistry, phenols, sometimes called phenolics, are a class of chemical compounds consisting of a hydroxyl group (—OH) bonded directly to an aromatic hydrocarbon group. The simplest of the class is phenol, C
6
H
5
OH
. Phenolic compounds are classified as simple phenols or polyphenols based on the number of phenol units in the molecule.

Polysaccharide polymeric carbohydrate molecules composed of long chains of monosaccharide units bound together by glycosidic linkages and on hydrolysis give the constituent monosaccharides or oligosaccharides

Polysaccharides are polymeric carbohydrate molecules composed of long chains of monosaccharide units bound together by glycosidic linkages, and on hydrolysis by amylase enzymes give the constituent monosaccharides or oligosaccharides. They range in structure from linear to highly branched. Examples include storage polysaccharides such as starch and glycogen, and structural polysaccharides such as cellulose and chitin.

Peroxisome Type of organelle

A peroxisome (IPA: [pɛɜˈɹɒksɪˌsoʊm]) is a membrane-bound organelle (formerly known as a microbody), found in the cytoplasm of virtually all eukaryotic cells. Peroxisomes are oxidative organelles. Frequently, molecular oxygen serves as a co-substrate, from which hydrogen peroxide (H2O2) is then formed. Peroxisomes owe their name to hydrogen peroxide generating and scavenging activities. They perform key roles in lipid metabolism and the conversion of reactive oxygen species. Peroxisomes are involved in the catabolism of very long chain fatty acids, branched chain fatty acids, bile acid intermediates (in the liver), D-amino acids, and polyamines, the reduction of reactive oxygen species – specifically hydrogen peroxide. – and the biosynthesis of plasmalogens, i.e., ether phospholipids critical for the normal function of mammalian brains and lungs They also contain approximately 10% of the total activity of two enzymes in the pentose phosphate pathway, which is important for energy metabolism. It is vigorously debated whether peroxisomes are involved in isoprenoid and cholesterol synthesis in animals. Other known peroxisomal functions include the glyoxylate cycle in germinating seeds ("glyoxysomes"), photorespiration in leaves, glycolysis in trypanosomes ("glycosomes"), and methanol and/or amine oxidation and assimilation in some yeasts.

Pectin Structural heteropolysaccharide contained in the primary cell walls of terrestrial plants and some algae

Pectin is a structural acidic heteropolysaccharide contained in the primary cell walls of terrestrial plants. Its main component is galacturonic acid, a sugar acid derived from galactose. It was first isolated and described in 1825 by Henri Braconnot. It is produced commercially as a white to light brown powder, mainly extracted from citrus fruits, and is used in food as a gelling agent, particularly in jams and jellies. It is also used in dessert fillings, medicines, sweets, as a stabilizer in fruit juices and milk drinks, and as a source of dietary fiber.

Lignin is a class of complex organic polymers that form key structural materials in the support tissues of vascular plants and some algae. Lignins are particularly important in the formation of cell walls, especially in wood and bark, because they lend rigidity and do not rot easily. Chemically, lignins are cross-linked phenolic polymers.

Rhamnose is a naturally occurring deoxy sugar. It can be classified as either a methyl-pentose or a 6-deoxy-hexose. Rhamnose occurs in nature in its L-form as L-rhamnose (6-deoxy-L-mannose). This is unusual, since most of the naturally occurring sugars are in D-form. Exceptions are the methyl pentoses L-fucose and L-rhamnose and the pentose L-arabinose.

Sinapinic acid chemical compound

Sinapinic acid, or sinapic acid (Sinapine - Origin: L. Sinapi, sinapis, mustard, Gr., cf. F. Sinapine.), is a small naturally occurring hydroxycinnamic acid. It is a member of the phenylpropanoid family. It is a commonly used matrix in MALDI mass spectrometry. It is a useful matrix for a wide variety of peptides and proteins. It serves well as a matrix for MALDI due to its ability to absorb laser radiation and to also donate protons (H+) to the analyte of interest.

Xylan A biopolymer with prevalence by biomass exceeded only by that of cellulose and lignin

Xylan is a group of hemicelluloses that represents the third most abundant biopolymer on Earth. It is found in plants, in the secondary cell walls of dicots and all cell walls of grasses.

Laccases are copper-containing oxidase enzymes found in many plants, fungi, and microorganisms. Laccases act on phenols and similar substrates, performing one-electron oxidations, leading to crosslinking. For example, laccases play a role in the formation of lignin by promoting the oxidative coupling of monolignols, a family of naturally occurring phenols. Other laccases, such as those produced by the fungus Pleurotus ostreatus, play a role in the degradation of lignin, and can therefore be classed as lignin-modifying enzymes. Laccases catalyze ring cleavage of aromatic compounds.

In enzymology, a feruloyl esterase (EC 3.1.1.73) is an enzyme that catalyzes the chemical reaction

Arabinoxylan is a hemicellulose found in both the primary and secondary cell walls of plants, including woods and cereal grains, consisting of copolymers of two pentose sugars: arabinose and xylose.

Phenolic acid

Phenolic acids or phenolcarboxylic acids are types of aromatic acid compound. Included in that class are substances containing a phenolic ring and an organic carboxylic acid function. Two important naturally occurring types of phenolic acids are hydroxybenzoic acids and hydroxycinnamic acids, which are derived from non-phenolic molecules of benzoic and cinnamic acid, respectively.

Triferulic acids, also known as dehydrotriferulic acids, are a type of oligomeric natural phenols formed from ferulic acid.

Decarboxylated 8,5-diferulic acid chemical compound

Decarboxylated 8,5'-diferulic acid is a molecule included in the group but is not a true diferulic acid. It is found in maize bran.

Root mucilage is made of plant-specific polysaccharides or long chains of sugar molecules. This polysaccharide secretion of root exudate forms a gelatinous substance that sticks to the caps of roots. Root mucilage is known to play a role in forming relationships with soil-dwelling life forms. Just how this root mucilage is secreted is debated, but there is growing evidence that mucilage derives from ruptured cells. As roots penetrate through the soil, many of the cells surrounding the caps of roots are continually shed and replaced. These ruptured or lysed cells release their component parts, which include the polysaccharides that form root mucilage. These polysaccharides come from the Golgi apparatus and plant cell wall, which are rich in plant-specific polysaccharides. Unlike animal cells, plant cells have a cell wall that acts as a barrier surrounding the cell providing strength, which supports plants just like a skeleton.

References

  1. M.Bunzel, J.Ralph and H.Steinhart (2004). "Phenolic compounds as cross-links of plant derived polysaccharides" (PDF). Czech J. Food Sci. 22: 64–67. Archived from the original (PDF) on 2013-12-03.
  2. Bunzel, M; Ralph, J; Brüning, P; Steinhart, H (2006). "Structural identification of dehydrotriferulic and dehydrotetraferulic acids isolated from insoluble maize bran fiber". Journal of Agricultural and Food Chemistry. 54 (17): 6409–18. doi:10.1021/jf061196a. PMID   16910738.
  3. J.Ralph, J.H.Grabber, R.D.Hatfield and G.Wende (1996). "New discoveries relating to diferulates". 1996 USDFRC Research Summary. pp. 70–71.CS1 maint: multiple names: authors list (link)
  4. Ralph, John; Quideau, Stéphane; Grabber, John H.; Hatfield, Ronald D. (1994). "Identification and synthesis of new ferulic acid dehydrodimers present in grass cell walls". Journal of the Chemical Society, Perkin Transactions 1 (23): 3485. doi:10.1039/P19940003485.
  5. Renger, Anja; Steinhart, H. (2000). "Ferulic acid dehydrodimers as structural elements in cereal dietary fibre". European Food Research and Technology. 211 (6): 422–428. doi:10.1007/s002170000201.
  6. H. Boskov Hansen; M. Andreasen; M. Nielsen; L. Larsen; Bach K. Knudsen; A. Meyer; L. Christensen; Å. Hansen (2002). "Changes in dietary fibre, phenolic acids and activity of endogenous enzymes during rye bread-making". European Food Research and Technology. 214: 33–42. doi:10.1007/s00217-001-0417-6.
  7. Parker, Mary L.; Ng, Annie; Smith, Andrew C.; Waldron, Keith W. (2000). "Esterified Phenolics of the Cell Walls of Chufa (Cyperus esculentusL.) Tubers and Their Role in Texture". Journal of Agricultural and Food Chemistry. 48 (12): 6284–91. doi:10.1021/jf0004199. PMID   11141285.
  8. Micard, V.; Grabber, J.H.; Ralph, J.; Renard, C.M.G.C.; Thibault, J.-F. (1997). "Dehydrodiferulic acids from sugar-beet pulp". Phytochemistry. 44 (7): 1365–1368. doi:10.1016/S0031-9422(96)00699-1.
  9. Renard, D; Lavenant-Gourgeon, L; Ralet, MC; Sanchez, C (2006). "Acacia senegal gum: Continuum of molecular species differing by their protein to sugar ratio, molecular weight, and charges". Biomacromolecules. 7 (9): 2637–49. doi:10.1021/bm060145j. PMID   16961328.
  10. Bunzel, Mirko; Allerdings, Ella; Ralph, John; Steinhart, Hans (2008). "Cross-linking of arabinoxylans via 8-8-coupled diferulates as demonstrated by isolation and identification of diarabinosyl 8-8(cyclic)-dehydrodiferulate from maize bran". Journal of Cereal Science. 47: 29–40. doi:10.1016/j.jcs.2006.12.005.
  11. Fry, SC; Willis, SC; Paterson, AE (2000). "Intraprotoplasmic and wall-localised formation of arabinoxylan-bound diferulates and larger ferulate coupling-products in maize cell-suspension cultures". Planta. 211 (5): 679–92. doi:10.1007/s004250000330. PMID   11089681.
  12. Nicolai Obel; Andrea Celia Porchia; Henrik Vibe Scheller (February 2003). "Intracellular feruloylation of arabinoxylan in wheat: Evidence for feruloyl-glucose as precursor". Planta. 216 (4): 620–629. doi:10.1007/s00425-002-0863-9. JSTOR   23387682. PMID   12569404.
  13. Geissmann, T.; Neukom, H. (1971). "Vernetzung von Phenolcarbonsäureestern von Polysacchariden durch oxydative phenolische Kupplung". Helvetica Chimica Acta. 54 (4): 1108–1112. doi:10.1002/hlca.19710540420.
  14. Garcia-Conesa, MT; Plumb, GW; Waldron, KW; Ralph, J; Williamson, G (1997). "Ferulic acid dehydrodimers from wheat bran: Isolation, purification and antioxidant properties of 8-O-4-diferulic acid". Redox report : communications in free radical research. 3 (5–6): 319–23. PMID   9754331.
  15. Hartley, Roy D.; Jones, Edwin C. (1976). "Diferulic acid as a component of cell walls of Lolium multiflorum". Phytochemistry. 15 (7): 1157–1160. doi:10.1016/0031-9422(76)85121-7.